Water-insoluble azo dyestuffs



Uite States atent fice Patented Dec, 18, 1%32 The present application is a continuationdn-part of copending application Ser. No. 671,4-i8, filed July 12, 1957, now abandoned, and relates to new water-insoluble azo dyestuffs and to a process for their production.

The new wateninsoluble azo dyestuils are suitable for dyeing secondary cellulose acetate and cellulose triacetate in the mass. A number of the dyestuffs also have affinity for cellulose ester fibers and synthetic polyarnide fibers, e.g. nylon and Pei-Ion (registered trademark), polyvinyl fibers, and terephthalic acid ester fibers, eg. Terylene, Dacron (registered trademarks). 'l' hey are applied to the latter named fibers at elevated temperature and preferably in the presence of compounds with dispersing action. Those dyestuffs which are sparingly soluble or insoluble in organic solvents can also be employed with success as pigmentsv A selection of the dyestuffs in question is suitable for the pigmentation of oils, lacquer media and synthetic resins. Some of them also dye wool and silk.

The disclosed dyestuffs are applied from suspension to the aforenamed fibers to give yellow-orange to violet dyeings which are characterized by excellent fastness to washing, sea Water, sublimation, perspiration, ironing, heat setting and gas fumes. The dyeings have good light tastness on polyamide fibers and very good to outstanding light fastness on the other fibers.

Spun-dyed shades exhibit good to very good fastness to light, water, washing, perspiration, cross dyeing, chlorination in alkaline medium, sublimation, oxalic acid, dry cleaning, gas fumes, rubbing, ironing, peroxide bleaching and heat setting.

The new water-insoluble azo dyestuffs correspond to the formula i K a, l M

R4N=N N\ 1 hero-canon, L y H wherein:

halogen, the methoxy, ethoxy, difluoromethyl, trifiuoromethyl, cyano or carballsoxy radical, or

where 3;, has the previously stated meaning, or a simple linkage when m stands for the figure 2, and

R, a mononuclear aromatic, a mononuclear heterocyclic or a dinuclear heterocyclic radical containing further substituents commonly present in azo dyestufis with the exception of Water-solubilizing groups.

Especially interesting dyestuffs are the monoazo dyestur'i's which correspond to the formula wherein y represents hydrogen, chlorine, methyl, trifiuoromethyl or an alkanoylamino radical having not more than 18 carbon atoms,

w represents hydrogen or methyl,

R represents ethyl, cyanoethyl, difiuoroethyl or trifiuoroethyl,

R represent phenyl, and

R represents a mononuclear aromatic, a mononuclear heterocyclic or a dinuclear heterocyclic radical substituted by chlorine, nitro, triiiuoromethyl or inethylsulfonyl,

and the disazo dyestuffs which correspond to the formula:

31 represents hydrogen, chlorine, methyl, nifiuoromethyl or an alkanoylamino radical having not more than 18 carbon atoms,

w represents hydrogen or methyl,

R represents phenyl, and

R represents a mononuclear aromatic, a mononuclear heterocyclic or a dinuclear heterocyclic radical substituted by chlorine, nitro, trifluorornethyl or methylsulfonyl.

The process for their production consists in coupling in moles of a diazo compound containing further substituents commonly present in azo dyestuffs with the exception of water-solubilizing groups with 1 mol of a tertiary amine of the formula II x M wherein x, y, R R R M and m possess the above named meanings.

Suitable diazo components free from water-solubilizing groups are aminobenzenes, aminothiazoles, aminothiodiazoles or aminobenzenethiazoles substituted by halogen atoms, nitro, acyl, cyano and/or alkylsulfonyl groups.

The diazo compound is coupled with the coupling component in acid medium, which may be buttered if desired.

In the following examples all parts and percentages are by weight. The temperatures are in degrees centigrade and the melting points are uncorrected.

EXAMPLE 1 17.5 parts of l-amino-2-chloro-4-nitrobenzene, 125 parts of water and 42.5 parts of hydrochloric acid are mixed together, stirred for some time and then diazotized by the addition of a solution of 7 parts of sodium nitrite and 25 parts of water at 0. The resulting diazo solution is given 0.5 part of arnidosultonic acid and then stirred for some time and filtered. The filtrate is united with a solution of 26 parts of the phenyl carbamic acid ester of 1-(N-ethyl-N-fl-hydroxyethyl)-amino3-methylbenzene, 100 parts of acetic acid and 200 parts of water at 0. Following this a solution of parts of sodium acetate in parts of 'water is added dropwise. After some time the coupling reaction is completed. The precipitated dyestufi is filtered 0E and dried.

The phenyl carbamic acid ester of the l-[4-(N-ethyl- N-fJ-hydroxyethyl) amino 2 methyl] phenylazo 2- chloro-4-nitrobenzene is obtained in good yield. The new product crystallizes from ethanol in attractive red crystals, dissolves in ethyl acetate or acetone with a red coloration and dyes cellulose acetate fibers in the spinning solution in scarlet shades.

The following procedure is used for dyeing cellulose acetate in the spinning solution:

100 parts of cellulose acetate are added to 400 parts of a solvent mixture of 93% acetone and 7% methanol. The mass is stirred for a short time and left overnight to swell. 0.5 part of the monoazo dyestuil obtainable according to Example 1 is dissolved in 60 parts of the same solvent mixture by simple agitation. This solution is added to the cellulose acetate solution and the mixture stirred in an open vessel until 60 parts of the solvent have evaporated. The dyed mass is pumped into the spinning pot and spun in the normal way. The filaments are dyed scarlet-red; they possess very good fastness properties.

When the same quantity of the above-named diazo compound is coupled with 30 parts of the phenyl carbamic acid ester of l-(N-fi-cyanoethyl-Il-fl-hydroxyethylamino-3-n1ethylbenzene in the same manner, a red dyestufi which melts at is obtained.

In the following Table 1 further valuable monoazo dyestuffs are described which may be obtained by suitable replacement of the diazo and coupling components used in Example 1. These dyestuffs have the general formula They are characterized in the table by the symbols R R and y and by their melting points.

aaos

Table 1 Ex. R4 1/ R5 LN .P., No. 0.

2..... SZ-chloro-l-nitro- Methyl..- Ethyl 186 phenyl. 3....- 4-nitr0phenyl Hydrogen. ..--.do 4. 0 ll/Icthyl--- 173 5. --..do.. Fvdrogen 184 G-.--. 2-chl0r0-4-methy1- Methyl-.- 138 sulfonylphenyl. 7 ..do ..do Phenyl carbamlc acid ethyl. 8.... 4-nitrophenyl ..do ..do 185 The following Table 2 contains further valuable monoazo dyestuffs corresponding to the formula They are obtainable in the manner described in the Example 1 and are characterized by the symbols R R and w in Columns (l) to (ill) and by the shade produced in solution-dyed cellulose acetate in Column (IV).

Table 2 x. No. R4 R 10 Shade in cellulose acetate 9.... 4-nitrophenyl-- Ethyl Hydrogen- Scarlet. .-.--do..-.. .-.-.do Methyl..- D0.

" 2-tritluorocthyl. 37... ---.do Methyl 38... 5-methylsulf0nyl- Ethyl benzothiazolyl 2.

2-chloroetl1yl..-

2-oyanoetl1yl.

Orange red.

methylsullonylphenyl. -do

n-Propyl Scarlet.

Table 3 contains valuable water-insoluble monoazo dyestufis which correspond to the formula W and are characterized by the symbols x, y, w, R and R in Columns (1) .to (V) and by the shade produced in solution-dyed cellulose acetate in Column (VI).

HaC-OzS- Table 3 Ex Shade in I y w R; R; cellulose acetate 46..-.- Hydrogen... Methyl Methyl Violet. 47.. .--.c o Ethyl Red-violet. 48.. Propyl Do. 49.. Butyl D0. 50.. 2-chloroethyl Red. 51.. Z-methoxyethyl. Red. 52.. Z-ethoxyethyl Red. 53 2-(earbomethoxy)-ethyl Scarlet red.

...do.... Hydarogen Methoxy. Ethoxy. Hydrogen...

'A'Iethoxy. Ethoizy Acctylarnino Propionylamium. Butyrylamino...- Ohloracctylarnino. 'lriiluoro-acetylamino .Docanoylamino Hcxndccanoylaminm. Octadecanoylemino.

2-phenylcarbaniinic acid ethyl ester- Ethyl EXAMPLE 79 20.5 parts of l-ainino-2-chloro-4-rnethylsulfonyloenzene, 125 parts of water and 42.5 parts of hydrochloric acid are mixed together, stirred for a short time and then diazotized by the addition of a solution of 7 parts of sodium nitrite and 25 parts of water at 0. To the resultant cliazo solution is added 0.5 part of amidosulfonic acid, and after further stirring the solution is filtered. The filtrate is united with a solution of 27 parts of the bisphenylcarbamic acid ester of N.N'-bis-phenyl-N.N-bis- (2-hydroxyethyl)-ethylene diamine in 250 parts of formic acid 80% at 0, after which a solution of 70 parts of sodium acetate in 100 parts of Water is added dropwise. After some time coupling is completed. The precipitated disazo dyestuif is filtered oil and dried. A good yield is obtained. The dyestutf dissolves in ethyl acetate 'With a red coloration and dyes cellulose acetate in the mass in scarlet-red shades.

EXAMPLE amine in parts of glacial acetic acid. After some time the coupling is completed. Upon further treatment a red dyestufi is obtained which when lee-crystallized from ethyl alcohol melts at 112 and dyes cellulose acetate in the mass in brilliant red shades of excellent fastness.

When the same quantity of the above-mentioned diazo compound is united with 42 parts of the bis-pl'ienylcar-= barnic acid ester of PIN-bis(2-hydroxyethy1)-aminohenzene, a red dyestuff is obtained with a melting point at and an acetone-solubility of 80 grams per liter. It dyes cellulose acetate in the mass in very fast and brilliant red shades.

in Table 4 are listed valuable disazo dyestuffs corresponding to the formula They are obtainable according to the indications given in Examples 79 and 80 and are characterized by the symhols w, 1, R and R in Columns (1) to (IV) and by the shade produced in solution-dyed cellulose acetate in Column (V).

Table 4 FY (W Ne w 11 Rs 1 .4 Shade m cellulose acetate Hydrogen Pheny1.. 2.4-bis-(1uethylsulionyD-pnenyl--. Orange. d o.... 4-nitr0-2eyanophenyl Red.

i do. 4-nitro-2-fiuorosullonylphenyl. Violet. ..d0. 4-nitro-2-triiluoror* thy1pheny1.... Orange. -..do.- 5-niti-othiazolyl- Violet. .-..do..... G-nitrobenzothiazoly1-2 Red. do. G-n:ethylsulionylbenzothiazolyl-Z.. Red.

do Violet. 0.0.. Scarlet-red iolet.

D0. D0. Blue-violet.

Red-violet.

aoeaaoe 8 Formulae of representative dyestuffs of the foregoing wherein: examples are m is one of the integers of 1 and 2;

EXAMPLE 1 x represents a member selected from the group consisting of hydrogen, chlorine, methyl, ethyl, bromine, methoxy First dyestuff: 5 and ethoxy;

Second dyestuff:

EXAMPLE 27 EXAMPLE 66 Cl Hto-ois- -s CHPCHS EXAMPLE 79 EXAMPLE 80 (LHPCHLMHN Having thus disclosed the invention what is claimed is: y represents a member selected from the group consisting 1. A water-insoluble azo dyestufi, free from carboxylic of hydrogen, chlorine, bromine, methyl, ethyl, trifluoroacid, sulfonic acid and sulfonamide groups, of the formethyl, methoxy, ethoxy and an alkanoylamino radical mula 70 having not more than 18 carbon atoms;

R1 1 M R represents an alkylene radical with from 1 to 4 carbon atoms; R4"N=N R represents an alkylene radical with from 2 to 4 car- R2O-CiNHR3 bon atoms;

0 m 75 R represents a member selected from the group consisting of phenyl, lower alkylphenyl, dimethylphenyl and (e) bis-methylsulfonyl-phenyl;

methoxyphenyl; (f) thiazolyl substituted with one negative substituent M represents a member selected from the group consistselected from the group consisting of chloro, nitro,

ing of hydrogen, chlorine, bromine, methoxy, ethoxy, fiuorosulfonyl, trifluoromethyl and cyano; and

difluoromethl, trifluoromethyl, cyano, a lower carbalk- 5 (g) benzothiazolyl substituted with one negative suboxy radical and the radical OCO-NH.R stituent selected from the group consisting of nitro Where R has the previously stated meaning when m and methylsulfonyl.

stands for the figure 1 and and represents a simple 2. The Water-insoluble azo dyestufi which corresponds linkage when m stands for the figure 2; and to the formula R represents a member selected from the group consist- 3. The Water-insoluble azo dyestufi which corresponds ing of; to the formula (a) phenyl substituted with from one to two negative 4. The Water-insoluble azo dyestutf which corresponds substituents independently selected from the group to the formula HgC-O2S CHe-CHr-CN consisting of chloro, nitro, fluorosulfonyl, trifluoro- 5. The Water-insoluble azo dyestufi which corresponds methyl and cyauo; to the formula HBCFWS /OH2CHrO-OOENO C-N= -N 9 Q Q N CH2--OHzOCO-HN (b) mone-methylsulfonyl-phenyl; 6. The Water-insoluble azo dyestufi' which corresponds -(c) methylsulfonyl-mononitrophenyl; to the formula References Cited in the file of this patent UNITED STATES PATENTS 2,238,486 Dickey et al. Apr. 15, 1941 2,677,698 Deutschman et a1 May 4, 1954 2,785,157 Straley et al. Mar. 12, 1957 2,967,858 Merian et a1. Ian. 10, 1961 3,007,915 Merian Nov. 7, 1961 

1. A WATER-INSOLUBLE AZO DYESTUFF, FREE FROM CARBOXYLIC ACID, SULFONIC ACID AND SULFONAMIDE GROUPS, OF THE FORMULA 